Allylamine, lithiated

Beak and co-workers have also produced the key alcohol intermediate 74 by the sparteine-mediated lithiation and conjugate addition of allylamines to nitroalkenes to give Z-enecarbamates in good yields with high enantio- and diastereoselectivty (Scheme 16). Thus treatment of the allylamine 87 with n-BuLi in the presence of (-)-sparteine followed by conjugate addition to nitroalkene 88 gave the desired enecarbamate 89 in... 

Structural studies on the mechanism of the THF-catalyzed vinylic lithiation of allylamine derivatives have been performed using 2D and diffusion-ordered NMR spectroscopy.10 NMR evidence has suggested that in THF the mixed aggregate has close contact between the alkene and the /S-CfG of n-BuLi, whereas in the absence of THF, the allyl chain appears to be pointed away from the nearest n-BuLi residues. 

Cl/Li exchange. Functional propargyllithium reagents, lithiated compounds containing acetal and allylamine are obtained from the corresponding chlorides. Many dichlorides undergo lithiation and then react with electrophiles. 

While intermolecular lithiation-substitutions of allylic amines are most commonly studied, (-)-sparteine mediated intramolecular substitution reactions of lithiated W-Boc-allylamines have also been developed. Treatment of allylic... 

P-Pinene, a byproduct of the wood and paper industry, is the starting material for an enantioselective synthesis of (i )-citronellal Thermal cycloreversion leads to myrcene. The allylamine obtained by lithiation of myrcene with butyllithium and diethylamine involving an intermediate lithium chelate rearranges stereoselectively in the presence of a chiral catalyst containing the BlNAP-ligand (2,2 -bis-(di-phenylphosphino)-l,r-binapthyl = BINAP) (telomerization) to the enamine, which then readily undergoes acid-catalyzed hydrolysis to (7 )-(+)-citronellal with high enantiomeric excess. 

The aza-analogous ring closure of lithiated 2-(alkenylidene)allylamines 391 affords 4,5-dihydroazepin-l-yllithiums (Scheme 1-305). " The replacement of a weak carbon-metal interaction by a stronger nitrogen-metal bond obviouslyly propels the reaction. 

---